CN109592980B - Low-temperature co-fired piezoelectric multilayer ceramic and preparation method thereof - Google Patents
Low-temperature co-fired piezoelectric multilayer ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-temperature co-fired piezoelectric multilayer ceramic, which has a structural general formula of PbxM3 1‑X〔(M4 1/3Nb 2/3)e(Co1/3Nb2/3)f(Zn1/3Nb2/3)gZr.Ti]O3+ wmol% Cuo with x =0.86-0.96, e =0.01-0.10, f =0.01-0.5, g =0.01-0.6, w = 0.05-2.5. The invention also provides a method for preparing the piezoelectric multilayer ceramic, and the method can be used for preparing low-temperature sintered piezoelectric multilayer ceramic with high piezoelectric constant, high quality factor, high electromechanical coupling coefficient, high dielectric constant and high capacity, and solves the problems that the conventional common piezoelectric ceramic has high sintering temperature and cannot be used for preparing high-capacity piezoelectric devices. The preparation method disclosed by the invention has the characteristics of simple process, no special equipment requirement, low cost, contribution to large-scale production of enterprises and the like, and can be used for various high-capacity piezoelectric device products such as piezoelectric buzzers and the like.
Description
Technical Field
The invention relates to a multilayer piezoelectric ceramic technology, in particular to a piezoelectric ceramic material capable of realizing low-temperature co-firing and a preparation method thereof.
Background
The sintering temperature of the existing piezoceramic material is 1250-1300 ℃, and the piezoceramic material is difficult to sinter into porcelain at the temperature of 900-950 ℃; the silver electrode material can volatilize when being sintered at 1250-1300 ℃, so that the multilayer lamination sintering can be realized only by using expensive silver palladium slurry as an electrode, and the cost of the piezoelectric multilayer ceramic element is greatly improved. Therefore, it is very important to research and manufacture the piezoelectric ceramic component capable of low temperature co-firing.
Generally speaking, when the piezoelectric ceramic material has a higher curie temperature, the static capacitance is lower, the dielectric loss is also larger, and the comprehensive performance is poorer; for piezoelectric devices, high capacitance is required, and high dielectric constant and electromechanical coupling coefficient are also required. Research shows that the sintering temperature of the bismuth laminated piezoelectric ceramic is more than 1250 ℃, but the piezoelectric coefficient is only 30 pC/N; and BiScO3-PbTiO3The system piezoelectric ceramic has optimal piezoelectric property (T)c≈430℃，d33400 pC/N), but the overall electrical performance is poor. Therefore, the high-voltage electrical constant (d) is developed with low sintering temperature, high use temperature (more than or equal to 220 ℃), and high piezoelectric constant33Not less than 450 pC/N), high electromechanical coupling coefficient (K)pNot less than 75%), higher dielectric constant (epsilon not less than 2600), excellent comprehensive electrical properties and high capacity, which is a difficult problem in the field of piezoelectric ceramics.
Disclosure of Invention
Aiming at the current situation that the existing piezoelectric ceramic material cannot have higher comprehensive piezoelectric performance at the same time of low sintering temperature and cannot meet the use requirement of a piezoelectric device, the invention provides a high-performance piezoelectric ceramic material which has low sintering temperature, high capacitance and good comprehensive piezoelectric performance and can be adjusted in a certain range, and in order to solve the technical problems, the technical scheme is as follows:
a low-temperature co-fired piezoelectric multilayer ceramic material has a structural general formula of PbxM3 1-X［(M4 1/3Nb2/3)e(Co1/3Nb2/3)f(Zn1/3Nb2/3)gZrTi］O3+ w mol% of CuO, where M3A modifying element which is a 3-valent metal, M4Is a 4-valent metal element, and the modified element M is La, K, Er,One or more of Yb; in the structural general formula, the value range of x is 0.86-0.96, the value range of e is 0.01-0.10, the value range of f is 0.01-0.5, the value range of g is 0.01-0.6, and the value range of w is 0.05-2.5.
The preparation method of the low-temperature co-fired piezoelectric multilayer ceramic comprises the following steps:
(1) mixing PbO and ZrO2、TiO2、Ni2O3、Nb2O5、Co2O3ZnO, CuO and oxides or salts of modified elements are weighed according to the mol ratio and then mixed to obtain powder;
(2) stirring the primary grinding material for 2.5-3.5 hours by using a water mill stirrer, wherein the weight ratio of the material to balls to water is 1:2: 0.6; drying the uniformly mixed powder in a drying oven at 150-170 ℃ for 10h, and then calcining and synthesizing the dried powder in a tunnel furnace at 800-850 ℃;
(3) sanding the secondary grinding material for 5.5-6.5 h by using a sanding machine, wherein the weight ratio of the material to the balls to the water is 1:2:0.6, and the granularity D is ensured50Reaching 1.0-1.4 μm; putting the sand grinding material into an oven at the temperature of 150-170 ℃ for baking for 19-21 h, naturally cooling the dried material to normal temperature, and sieving the material with a 120-mesh vibrating screen to prepare material powder to be molded;
(4) adding an adhesive, a dispersing agent, a defoaming agent and water into the powder according to a certain proportion, uniformly mixing and ball-milling, carrying out tape casting on a casting machine for 23-25 hours, cutting the formed diaphragm into a certain size, printing silver electrodes, and then laminating according to the required number of layers; carrying out isostatic pressing on the laminated membrane in an isostatic pressing machine for 35-45 minutes, then placing the membrane on an alumina plate with the content of 99%, sintering the membrane in a tunnel furnace at 900-950 ℃, and stripping the membrane after sintering;
(5) printing silver paste with the required diameter and thickness of 0.003-0.007 mm on the upper surface and the lower surface of the prepared laminated ceramic sheet by using a screen printing method, drying in a tunnel drying furnace at 200-300 ℃, putting on a zirconia backing plate, and burning silver in a tunnel furnace at 780-820 ℃ to prepare a multilayer silver-coated ceramic sheet; putting the multilayer silver-coated ceramic wafer into a polarization device at the temperature of 95-105 ℃ to polarize for 25-35 minutes under the voltage of 2-3.6 kV/mm, and preparingHas the general formula of PbxM3 1-X［(Ni1/3Nb2/3)e(Co1/3Nb2/3)f(Zn1/ 3Nb2/3)gZrTi］O3A multilayer piezoelectric ceramic coated silver sheet of + wmol% CuO.
The invention has the beneficial effects that: the material has low sintering temperature, high capacitance and excellent comprehensive performance, and is composite perovskite structure PbxM3 1-X［(Ni1/3Nb2/3)e(Co1/3Nb2/3)f(Zn1/3Nb2/3)gZrTi］O3The novel piezoelectric ceramic material of CuO with the mol% of + wmol solves the problems that the prior piezoelectric ceramic material can not be sintered at low temperature, has good performance and meets the use requirement of electrical performance. The piezoelectric material can meet the low-temperature co-firing requirement of multilayer piezoelectric ceramics, improve the capacitance of the piezoelectric ceramics, greatly reduce the cost, has higher piezoelectric constant (450-600 pC/N), electromechanical coupling coefficient of 75-85% and dielectric constant of 2600-3300, and can meet the requirements of various high-capacity piezoelectric device products such as piezoelectric buzzers and the like.
Detailed Description
Example 1
A low-temperature co-fired piezoelectric multilayer ceramic material has a structural general formula of PbxM3 1-X［(M4 1/3Nb2/3)e(Co1/3Nb2/3)f(Zn1/3Nb2/3)gZr.Ti］O3+ w mol% of CuO, where M3Is a modifying element of a 3-valent metal, M4Is a 4-valent metal element; in the structural general formula of the piezoelectric material, the value range of x is 0.86, the value range of e is 0.10, the value range of f is 0.01, the value range of g is 0.6, and the value range of w is 0.05. Wherein the modified element M in the low-temperature co-fired piezoelectric multilayer ceramic material is La.
The preparation method of the low-temperature co-fired piezoelectric multilayer ceramic comprises the following steps:
(1) mixing PbO and ZrO2、TiO2、Ni2O3、Nb2O5、Co2O3ZnO, CuO and oxides or salts of modified elements are weighed according to the mol ratio and then mixed to obtain powder;
(2) stirring the first grinding material in a water mill stirrer for 2.5h, wherein the weight ratio of the material to the balls to the water is 1:2:0.6, and uniformly mixing; drying the uniformly mixed powder in an oven at 170 ℃ for 10 h; calcining and synthesizing the dried powder in a tunnel furnace at 800 ℃;
(3) sanding the secondary abrasive material for 6.5h by using a sanding machine, wherein the weight ratio of the material to the balls to the water is 1:2:0.6, and the granularity D is ensured50Up to 1.0 μm; putting the sand grinding material into an oven at 170 ℃ for baking for 19 hours to fully dry the sand grinding material; naturally cooling the dried material to normal temperature, and sieving the dried material with a 120-mesh vibrating screen to prepare material powder to be molded;
(4) adding an adhesive, a dispersing agent, a defoaming agent and water into the powder according to a certain proportion, uniformly mixing and ball-milling, carrying out tape casting on a casting machine for 24 hours, cutting the formed diaphragm into a certain size, printing a silver electrode, and then laminating according to the required number of layers; carrying out isostatic pressing on the laminated membrane in an isostatic pressing machine for 45 minutes, then placing the membrane on an alumina plate with the content of 99 percent, sintering the membrane in a tunnel furnace at 900 ℃, and stripping the membrane after sintering;
(5) printing silver paste with required diameter and thickness of 0.007 mm on the upper and lower surfaces of the prepared laminated ceramic sheet by using a screen printing method, drying in a tunnel drying furnace at 200 ℃, putting on a zirconia backing plate, and burning silver in the tunnel furnace at 820 ℃ to prepare a multi-layer silver-coated ceramic sheet; putting the multilayer silver-coated ceramic sheet into a polarizing device at 95 ℃ and polarizing for 25 minutes under the voltage of 3.6kV/mm to prepare the material with the general formula of PbxM3 1-X［(Ni1/3Nb2/3)e(Co1/3Nb2/3)f(Zn1/3Nb2/3)gZrTi］O3A multilayer piezoelectric ceramic coated silver sheet of + wmol% CuO.
Example 2
A low-temperature co-fired piezoelectric multilayer ceramic material has a structural general formula of PbxM3 1-X［(M4 1/3Nb2/3)e(Co1/3Nb2/3)f(Zn1/3Nb2/3)gZrTi］O3+ w mol% of CuO, where M3Is a modifying element of a 3-valent metal, M4Is a 4-valent metal element; in the structural general formula of the piezoelectric material, the value range of x is 0.96, the value range of e is 0.01, the value range of f is 0.5, the value range of g is 0.01, and the value range of w is 2.5. Wherein the modified element M in the low-temperature co-fired piezoelectric multilayer ceramic material is Er.
The preparation method of the low-temperature co-fired piezoelectric multilayer ceramic comprises the following steps:
(1) mixing PbO and ZrO2、TiO2、Ni2O3、Nb2O5、Co2O3ZnO, CuO and oxides or salts of modified elements are weighed according to the mol ratio and then mixed to obtain powder;
(2) stirring the primary grinding material for 3.5 hours by using a water mill stirrer, wherein the weight ratio of the material to the balls to the water is 1:2:0.6, and uniformly mixing; drying the uniformly mixed powder in a drying oven at 150 ℃ for 10 h; calcining and synthesizing the dried powder in a tunnel furnace at 850 ℃;
(3) sanding the secondary abrasive material for 5.5h by using a sanding machine, wherein the weight ratio of the material to the balls to the water is 1:2:0.6, and the granularity D is ensured50Reaching 1.2 μm; putting the sand grinding material into an oven at 170 ℃ for baking for 19 hours to fully dry the sand grinding material; naturally cooling the dried material to normal temperature, and sieving the dried material with a 120-mesh vibrating screen to prepare material powder to be molded;
(4) adding an adhesive, a dispersing agent, a defoaming agent and water into the powder according to a certain proportion, uniformly mixing and ball-milling, carrying out tape casting on a casting machine for 24 hours, cutting the formed diaphragm into a certain size, printing a silver electrode, and then laminating according to the required number of layers; carrying out isostatic pressing on the laminated membrane in an isostatic pressing machine for 35 minutes, then placing the membrane on an alumina plate with the content of 99 percent, sintering the membrane in a tunnel furnace at 950 ℃, and stripping the membrane after sintering;
(5) the upper and lower surfaces of the prepared laminated ceramic sheet are printed by silk screenSilver paste with the diameter and the thickness of 0.003 mm is required to be dried in a tunnel drying furnace at 300 ℃, and is put on a zirconia backing plate to be sintered at 780 ℃ in the tunnel furnace to prepare a multilayer silver-coated ceramic plate; putting the multilayer silver-coated ceramic sheet into a 105 ℃ polarization device, and polarizing for 35 minutes under the voltage of 2kV/mm to prepare the material with the general formula of PbxM3 1-X［(Ni1/3Nb2/3)e(Co1/3Nb2/3)f(Zn1/3Nb2/3)gZrTi］O3A multilayer piezoelectric ceramic coated silver sheet of + wmol% CuO.
Example 3
A low-temperature co-fired piezoelectric multilayer ceramic material has a structural general formula of PbxM3 1-X［(M4 1/3Nb2/3)e(Co1/3Nb2/3)f(Zn1/3Nb2/3)gZrTi］O3+ w mol% of CuO, where M3Is a modifying element of a 3-valent metal, M4Is a 4-valent metal element; in the structural general formula of the piezoelectric material, the value range of x is 0.90, the value range of e is 0.08, the value range of f is 0.35, the value range of g is 0.4, and the value range of w is 2.0. Wherein the modified element M in the low-temperature co-fired piezoelectric multilayer ceramic material is Yb.
The preparation method of the low-temperature co-fired piezoelectric multilayer ceramic comprises the following steps:
(1) mixing PbO and ZrO2、TiO2、Ni2O3、Nb2O5、Co2O3ZnO, CuO and oxides or salts of modified elements are weighed according to the mol ratio and then mixed to obtain powder;
(2) stirring the primary grinding material for 3.0 hours by using a water mill stirrer, wherein the weight ratio of the material to the balls to the water is 1:2:0.6, and uniformly mixing; drying the uniformly mixed powder in a 160 ℃ drying oven for 10 hours; calcining and synthesizing the dried powder in a tunnel furnace at 820 ℃;
(3) sanding for the second time for 6.0h by using a sanding machine, wherein the weight ratio of the material to the balls to the water is 1:2:0.6, and the granularity D is ensured50Reaching 1.4 μm;putting the sand grinding material into a 160 ℃ oven for baking for 20 hours to fully dry the sand grinding material; naturally cooling the dried material to normal temperature, and sieving the dried material with a 120-mesh vibrating screen to prepare material powder to be molded;
(4) adding an adhesive, a dispersing agent, a defoaming agent and water into the powder according to a certain proportion, uniformly mixing and ball-milling, carrying out tape casting on a casting machine for 23 hours, cutting the formed diaphragm into a certain size, printing silver electrodes, and then laminating according to the required number of layers; isostatic pressing the laminated membrane in an isostatic press for 40 minutes; then placing the aluminum plate on an alumina plate with the content of 99 percent, sintering the aluminum plate in a tunnel furnace at the temperature of 920 ℃, and stripping the aluminum plate after sintering;
(5) printing silver paste with required diameter and thickness of 0.005 mm on the upper and lower surfaces of the prepared laminated ceramic sheet by using a screen, drying in a tunnel drying furnace at 250 ℃, putting on a zirconia backing plate, and burning the silver in a tunnel furnace at 800 ℃ to prepare a multilayer silver-coated ceramic sheet; putting the multilayer silver-coated ceramic sheet into a 100 ℃ polarization device, and polarizing for 30 minutes under the voltage of 2.6kV/mm to prepare the material with the general formula of PbxM3 1-X［(Ni1/3Nb2/3)e(Co1/3Nb2/3)f(Zn1/3Nb2/3)gZrTi］O3A multilayer piezoelectric ceramic coated silver sheet of + wmol% CuO.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (2)
1. A low-temperature co-fired piezoelectric multilayer ceramic material is characterized in that the structural general formula of the low-temperature co-fired piezoelectric multilayer ceramic material is as follows: pbxM3 1-X［(M4 1/3Nb2/3)e(Co1/3Nb2/3)f(Zn1/3Nb2/3)gZrTi］O3+ w mol% of CuO, where M3A modifying element which is a 3-valent metal, M4The modified element M is a 4-valent metal element, and is one or more of La, K, Er and Yb; in the structural general formula, the value range of x is 0.86-0.96, the value range of e is 0.01-0.10, the value range of f is 0.01-0.5, the value range of g is 0.01-0.6, and the value range of w is 0.05-2.5.
2. The preparation method for realizing the low-temperature co-fired piezoelectric multilayer ceramic of claim 1 is characterized by comprising the following steps of:
(1) mixing PbO and ZrO2、TiO2、Ni2O3、Nb2O5、Co2O3ZnO, CuO and oxides or salts of modified elements are weighed according to the mol ratio and then mixed to obtain powder;
(2) stirring the primary grinding material for 2.5-3.5 hours by using a water mill stirrer, wherein the weight ratio of the material to balls to water is 1:2: 0.6; drying the uniformly mixed powder in a drying oven at 150-170 ℃ for 10h, and then calcining and synthesizing the dried powder in a tunnel furnace at 800-850 ℃;
(3) sanding the secondary grinding material for 5.5-6.5 h by using a sanding machine, wherein the weight ratio of the material to the balls to the water is 1:2:0.6, and the granularity D is ensured50Reaching 1.0-1.4 μm; putting the sand grinding material into an oven at the temperature of 150-170 ℃ for baking for 19-21 h, naturally cooling the dried material to normal temperature, and sieving the material with a 120-mesh vibrating screen to prepare material powder to be molded;
(4) adding an adhesive, a dispersing agent, a defoaming agent and water into the powder according to a certain proportion, uniformly mixing and ball-milling, carrying out tape casting on a casting machine for 23-25 hours, cutting the formed diaphragm into a certain size, printing silver electrodes, and then laminating according to the required number of layers; carrying out isostatic pressing on the laminated membrane in an isostatic pressing machine for 35-45 minutes, then placing the membrane on an alumina plate with the content of 99%, sintering the membrane in a tunnel furnace at 900-950 ℃, and stripping the membrane after sintering;
(5) screen printing silver paste with required diameter and thickness of 0.003-0.007 mm on the upper surface and the lower surface of the prepared laminated ceramic sheetDrying in a tunnel drying furnace at the temperature of 200-300 ℃, putting on a zirconia backing plate, and burning silver in the tunnel furnace at the temperature of 780-820 ℃ to prepare a multilayer silver-coated ceramic sheet; putting the multilayer silver-coated ceramic wafer into a polarization device at the temperature of 95-105 ℃ and polarizing for 25-35 minutes under the voltage of 2-3.6 kV/mm to prepare the material with the general formula of PbxM3 1-X［(Ni1/3Nb2/3)e(Co1/3Nb2/3)f(Zn1/ 3Nb2/3)gZrTi］O3A multilayer piezoelectric ceramic coated silver sheet of + wmol% CuO.
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| CN113072362A (en) * | 2020-10-15 | 2021-07-06 | 中科传感技术(青岛)研究院 | Sintering method for protecting surface electrode of multilayer piezoelectric ceramic piece |
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